CN101456078A - Preparation method of nano nickel copper zinc ferrite powder - Google Patents
Preparation method of nano nickel copper zinc ferrite powder Download PDFInfo
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- CN101456078A CN101456078A CNA2009100736211A CN200910073621A CN101456078A CN 101456078 A CN101456078 A CN 101456078A CN A2009100736211 A CNA2009100736211 A CN A2009100736211A CN 200910073621 A CN200910073621 A CN 200910073621A CN 101456078 A CN101456078 A CN 101456078A
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Abstract
The invention relates to a method for preparing nano-scale nickel-copper-zinc-iron oxide powder, which comprises the following steps: using nickel sulfate, copper sulfate, zinc sulfate and ferrous sulfate as raw materials, ammonium oxalate as co-precipitation agent, high molecular material plasmosan as dispersant, deionized water as solvent and anhydrous ethyl alcohol as washing agent to prepare nickel sulfate solution, copper sulfate solution, zinc sulfate solution, ferrous sulfate solution and ammonium oxalate solution through selecting chemical substances; and under the heating state at the temperature of 50 DEG C in a water bathtub, in four flasks, dripping the plasmosan solution and the nickel-copper-zinc-iron mixed solution into the ammonium oxalate solution, stirring the mixture by magnetic force, and mixing the solutions fully to prepare co-precipitation solution, and finally obtaining the nano-scale nickel-copper-zinc-iron oxide powder through vacuum filtering, washing, filtering, vacuum drying and calcining at the temperature of 800 DEG C, wherein the particle diameter of the powder is 50 to 80 nanometers, and the saturation intensity is 52eum/g. The method has the advantages of short process flow, high yield up to 98.33 percent and good product purity, and can be used for manufacturing sheet type devices of electronic elements.
Description
Technical field
The present invention relates to a kind of preparation method of nickel copper zinc ferrite powder, belong to the technical field of electronic component chip inductor device material preparation.
Background technology
Soft magnetic ferrite be develop the earliest, a most widely used class Ferrite Material, along with the application of microelectronic circuit, surface mounted technology SMT and constantly perfect, electronic system product is more and more to the development of light, thin, short, little aspect, the miniaturization of electronic equipment must relate to the miniaturization of electronic devices and components.
As the resistor of passive electronic components, the chip type of capacitor is technology most widely used, with fastest developing speed, chip device can not only make miniaturization of electronic products, and can realize the increasingly automated of complete machine, the application of chip device, make the manufacture of electronic product that great variety take place, structure, material to chip device have also proposed new requirement, and how for example miniaturization, high frequencyization, low-loss etc. prepare chip device and material and become crucial research topic.
The size of electronics chip device is more and more littler, stack-up type electric capacity, the size of resistance has reached 1005 (1.0 * 0.5mm) model levels, but the slower development of solenoid, (3.2 * 1.6mm) models develop into 2012 models by 3216, this be since the stack-up type solenoid by the argent lead, soft magnetic ferrite is formed, inner silver-colored lead and ferrite sintering simultaneously are prone to broken string, problems such as cavity and magnetic weaken, so must just can finish in low-temperature sintering, normally used low temperature drop firing method has been sacrificed more magnetic property, as the main dielectric material that uses in the high frequency chip inductor device---nickel-copper-zinc ferrite has been subjected to the generally attention of domestic and international academia, prepares in low-temperature sintering at present and also has a lot of drawbacks and deficiency in the nickel-copper-zinc ferrite soft magnetic materials.
For example: application number is that 200510135937.0 " a kind of preparation method who solves inductance coil with low temperature sintered ferrite " patent, application number are 200710124962.8 " a kind of nickel-copper-zinc ferrite manufacture method ", on preparation process, the selection of material, preparation parameter, use value, all there is deficiency, also has some to need to discuss, inquire into the content of research.
Summary of the invention
Goal of the invention
Purpose of the present invention is exactly at disadvantages of background technology, a kind of nickel-copper-zinc ferrite material and preparation method of chip inductor device use of electronic component are provided, with chemical coprecipitation, low-temperature sintering method synthesis nano nickel copper zinc ferrite powder, with magnetic property and the mechanical strength that increases substantially nickel-copper-zinc ferrite.
Technical scheme
The chemical substance material that the present invention uses is nickelous sulfate, copper sulphate, zinc sulfate, ferrous sulfate, ammonium oxalate, deionized water, absolute ethyl alcohol, and its combination matching consumption is as follows: with gram, milliliter is measurement unit
Nickelous sulfate: NiSO
42.629g ± 0.001g
Copper sulphate: CuSO
42.500g ± 0.001g
Zinc sulfate: ZnSO
48.627g ± 0.001g
Ferrous sulfate: FeSO
427.805g ± 0.001g
Deionized water: H
2O 440ml ± 5ml
Absolute ethyl alcohol: C
2H
6O 50ml ± 2ml
Polyvinylpyrrolidone: [C
6H
9NO]
n0.670g ± 0.0005g
Ammonium oxalate: (NH
4)
2C
2O
425.582g ± 0.0001g
The preparation method is as follows:
(1) selected chemical substance material
The chemical substance material that preparation is used will carry out selected, and carries out purity control:
Magnetic acid nickel: 99.5%
Magnetic acid copper: 99.5%
Magnetic acid zinc: 99.5%
Magnetic acid is ferrous: 99.5%
Deionized water: 99.99%
Absolute ethyl alcohol: 99.7%
Polyvinylpyrrolidone: 99.9%
Ammonium oxalate: 99.8%
(2) preparing metal salt working solution
1. nickelous sulfate powder 2.629g ± 0.001g is placed beaker, add deionized water 13.3ml ± 0.1ml, stir 5min, become: nickel sulfate solution NiSO with agitator
46H
2O, mol ratio is 0.01mol;
2. copper sulphate powder 2.500g ± 0.001g is placed beaker, add deionized water 13.3ml ± 0.1ml, stir 5min, become: copper sulfate solution CuSO with agitator
45H
2O, mol ratio is 0.01mol;
3. zinc sulphate powder 8.627g ± 0.001g is placed beaker, add deionized water 40ml ± 0.4ml, stir 5min, become: zinc sulfate solution ZnSO with agitator
47H
2O, mol ratio is 0.03mol;
4. ferrous sulfate powder 27.805g ± 0.001g is placed beaker, add deionized water 133.3ml ± 1.4ml, stir 5min, become: ferrous sulfate aqueous solution FeSO with agitator
47H
2O, mol ratio is 0.1mol;
5. synthesis of metallic salt working solution
Nickel sulfate solution, copper sulfate solution, zinc sulfate solution, the ferrous sulfate aqueous solution of configuration are respectively placed the molten device of mixing, evenly stir 2min with oscillating agitator, make its mixing, become: nickelous sulfate+copper sulphate+zinc sulfate+ferrous sulfate quaternary mixed aqueous solution, standby;
(3) preparation ammonium oxalate precipitated liquid
25.582g ± 0.001g places beaker with ammonium oxalate, adds deionized water 240ml ± 2.4ml, stirs 10min with agitator, becomes: the ammonium oxalate aqueous solution (NH
4)
2C
2O
4H
2O, mol ratio is 0.18mol;
Add polyethylene of dispersing agent pyrrolidones 0.670g ± 0.0005g, and stir;
(4) coprecipitated reaction
1. the ammonium oxalate aqueous solution is placed four-hole boiling flask;
2. four-hole boiling flask is placed cleansing bath tub;
3. water-soluble cylinder is placed on the electric jacket;
4. insert thermometer, dropping funel, agitator, escape pipe on the four-hole boiling flask successively;
5. the ammonium oxalate aqueous solution is placed in the four-hole boiling flask, polyethylene of dispersing agent pyrrolidones 0.670g is Powdered herein, directly puts into when joining ammonium oxalate solution;
6. open the ammonium oxalate aqueous solution in electric jacket, heated water bath cylinder and the four-hole boiling flask, solution temperature rises to 50 ℃ ± 2 ℃;
7. drip the ambrose alloy zinc-iron quaternary aqueous solution
The quaternary aqueous solution is placed addition funnel, and rate of addition 10ml/min drips time 20min;
8. limit heating, limit drip, stir on the limit, and mixing speed 350r/min makes it fully mix, dissolve, time 120min ± 10min;
9. the concentration of metal sulfate and ammonium oxalate is 0.75mol/L, and the mol ratio of metal sulfate and ammonium oxalate is 1:1.2;
10. chemical reaction
Under ammonium oxalate aqueous solution heated condition, dripping under the quaternary mixed aqueous solution state, dripping under the polyethylene of dispersing agent pyrrolidones state, in whipping process chemical reaction will take place, reaction equation is as follows:
In the formula:
(NiCuZn) Fe
2(C
2O
4)
36H
2O: ambrose alloy zinc-iron oxalate mixtures
(5) vacuum filtration
Coprecipitated reacted mixed solution is placed Buchner funnel, Buchner funnel is placed on the vacuum filtration bottle;
In Buchner funnel, put three layers of middling speed qualitative filter paper, then coprecipitated reaction mixture is poured on the qualitative filter paper;
Open suction filter pump, waste liquid is evacuated in the filter flask, and the product filter cake is kept somewhere on the filter paper;
(6) washing, filtration
Absolute ethyl alcohol 10ml is placed on the product filter cake of funnel flushing, filtration;
Washing, filtration repeat 5 times;
(7) vacuum drying
Product filter cake after washing, the filtration is collected in the rustless steel container, and places vacuum drying chamber to carry out drying, vacuum is 1000Pa, and baking temperature is 80 ℃ ± 2 ℃, and be 1440min ± 10min drying time;
After the drying, get the product powder, that is: yellow, presoma product: ambrose alloy zinc-iron oxalate mixtures;
(8) calcining
The calcining of product powder is to carry out in the horizontal-type high temperature Muffle furnace;
The product powder is placed the ceramic product boat;
The product boat is placed Muffle furnace, and sealing;
Open not calcining furnace of horse, temperature rises to 200 ℃ by 20 ℃, 10 ℃/min of programming rate, at this temperature constant temperature insulation 120min ± 10min, eliminate micro-moisture and oxalates presoma in conjunction with water;
Continue to be warming up to 800 ℃ ± 10 ℃ then, 20 ℃/min of programming rate, constant temperature insulation 120min ± 10min;
Open calcining furnace, take out product boat and product powder;
Product boat and product powder are placed the pure air environment, naturally cool to 20 ℃ ± 3 ℃, get end product powder, that is: bronzing nickel copper zinc ferrite powder after the cooling;
To produce calcination reaction in sintering process, reaction equation is as follows:
In the formula: (NiC
uZ
n) Fe
2O
4: nickel copper zinc ferrite powder
CO
2: carbon dioxide
O: oxygen
(9) detect, chemically examine, analyze, characterize
Pattern, color and luster, composition, full phase constitution structure, Chemical Physics performance to the product powder of preparation are chemically examined, analyze, are characterized;
Carry out the analysis of oxalates presoma calcining and decomposing with differential thermal analysis meter;
Carry out the magnetic property analysis with vibrating specimen magnetometer;
Carrying out particle morphology with transmission electron microscope measures;
Carry out nickel-copper-zinc ferrite spinelle material phase analysis with X-ray diffractometer;
The product pattern is: bronzing, graininess powder, and the powder diameter is: 50-80nm; The full intensity of magnetization: the 52emu/g that closes;
(10) store
Nickel copper zinc ferrite powder to preparation places water white glass container, airtight storage, and clean environment wants waterproof, protection against the tide, acid-proof alkali salt to corrode 20 ℃ ± 3 ℃ of storage temperatures, relative humidity≤10%.
The preparation of described nickel-copper-zinc ferrite is to be raw material with nickelous sulfate, copper sulphate, zinc sulfate, ferrous sulfate, is coprecipitated dose with ammonium oxalate, is dispersant with the macromolecular material polyvinylpyrrolidone, is solvent with the deionized water, is washing agent with the absolute ethyl alcohol.
The calcining of described nickel copper zinc ferrite powder is carried out in the high temperature Muffle furnace, the micro-moisture evaporating temperature is 200 ℃ ± 10 ℃, the constant temperature temperature retention time is 120min ± 10min, and calcining heat is 800 ℃ ± 10 ℃, and constant temperature insulation time of repose is 120min ± 10min.
The pattern of described nickel copper zinc ferrite powder is the bronzing powder, powder particle diameter 50-80nm, and saturation magnetization is 52emu/g.
The coprecipitated reaction of described preparation nickel-copper-zinc ferrite is carried out in cleansing bath tub, four-hole boiling flask, the bottom of cleansing bath tub 1 is an electric jacket 2, the top of cleansing bath tub 1 is four-hole boiling flask 3, four-hole boiling flask 3 tops are provided with thermometer, dropping funel 5 and control valve 13, magnetic stirring apparatus 6, escape pipe 7 from left to right successively, and are reinforced by 14 sealings of tapering plug; Electric jacket 2 is provided with LCDs 12, magnetic agitation controller 11, electric controller 10; The cleansing bath tub 1 built-in bath water 8 that discharges water, in the four-hole boiling flask 3 is ammonium oxalate solution, successively put polyvinylpyrrolidonesolution solution, ambrose alloy zinc-iron quaternary mixed solution 9 in the dropping funel 5, being added dropwise to complete back four-hole boiling flask 3 interior solution is: ammonium oxalate solution+ambrose alloy zinc-iron quaternary mixed liquor+polyvinylpyrrolidone aqueous solution, promptly coprecipitated solution; Escape pipe 7 is discharged carbon dioxide.
Beneficial effect
The present invention compares with background technology has tangible advance, it is with nickelous sulfate, copper sulphate, zinc sulfate, ferrous sulfate is a raw material, with ammonium oxalate is coprecipitated dose, with the macromolecular material polyvinylpyrrolidone is dispersant, with the deionized water is solvent, with the absolute ethyl alcohol is washing agent, by selected raw chemical material, the preparation nickel sulfate solution, copper sulfate solution, zinc sulfate solution, ferrous sulfate aqueous solution, the ammonium oxalate aqueous solution, under 50 ℃ of heated conditions of cleansing bath tub, in four-hole boiling flask, in ammonium oxalate solution, drip polyvinylpyrrolidonesolution solution, ambrose alloy zinc-iron quaternary mixed liquor, magnetic agitation, fully mix, make coprecipitated liquid, pass through vacuum filtration, washing, filter, vacuum drying, 800 ℃ of calcinings, finally make nano nickel copper zinc ferrite powder, the powder particle diameter can reach 50-80nm, saturation magnetization 52emu/g, and this preparation method's technological process is short, the magnetic nano-particle particle is little, uniform crystal particles, the production yield rate height, production yield rate can reach 98.33%, can be widely used for making the chip device of electronic component, be the very good method for preparing nickel copper zinc ferrite powder.
Description of drawings
Fig. 1 is preparation technology's flow chart
Fig. 2 is coprecipitated solution state figure for cleansing bath tub prepares
Fig. 3 is the state diagram of coprecipitated solution for vacuum suction filtration
Fig. 4 is nickel copper zinc ferrite powder calcined state figure
Fig. 5 is nickel-copper-zinc ferrite calcining heat and time coordinate graph of a relation
Fig. 6 amplifies 100,000 times of shape appearance figures for nickel copper zinc ferrite powder
Fig. 7 is nickel copper zinc ferrite powder diffracted intensity figure
Fig. 8 is nickel-copper-zinc ferrite hysteresis curve figure
Shown in the figure, list of numerals is as follows:
1, cleansing bath tub, 2, electric jacket, 3, four-hole boiling flask, 4, thermometer, 5, dropping funel, 6, magnetic stirring apparatus, 7, escape pipe, 8, water-bath water, 9, ambrose alloy zinc-iron quaternary mixed liquor, 10, electric controller, 11, the magnetic agitation controller, 12, LCDs, 13, control valve, 14, the tapering plug, 15, ammonium oxalate solution+quaternary mixed liquor+polyvinylpyrrolidone mixed liquor, 16, ammonium oxalate solution, 17, bottle,suction, 18, suction filter pump, 19, Buchner funnel, 20, the product filter cake, 21, coprecipitated mixed liquor, 22, waste liquid, 23, qualitative filter paper, 24, heater, 25, the product boat, 26, furnace chamber, 27, pore, 28, horse is calcining furnace not, and 29, the product powder.
The specific embodiment
The present invention will be further described below in conjunction with accompanying drawing:
Shown in Figure 1, be preparation technology's flow chart, strict and undertaken, according to the order of sequence operation by processing step.
The value of the chemical substance that preparation is used is to determine by the scope that sets in advance, and is measurement unit with gram, milliliter, minute, when industrialization is produced, with kilogram, liter, hour be measurement unit.
It is clean that the four-hole boiling flask that preparation is used, cleansing bath tub, dropping funel, magnetic stirring apparatus, vacuum filtration bottle, Buchner funnel, container, calcining furnace, product boat etc. will keep, and must not pollute, in case generate accessory substance.
The preparation of nickel sulfate solution, copper-bath, solution of zinc sulfate, copperas solution, ammonium oxalate solution wants strict value, scope by setting to carry out, and each parameter is wanted accurately, in order to avoid influence chemical reaction.
The calcining of product powder is not carried out in the calcining furnace horizontal horse, carry out low temperature calcination with 200 ℃ ± 10 ℃ earlier, eliminate the powder micro-moisture, and then rise to 800 ℃ ± 10 ℃, constant temperature insulation 120min ± 10min takes out then and be cooled to 20 ℃ ± 3 ℃ in pure air.
The check and analysis of product powder, sign, storage want strictness to carry out.
Nickel copper zinc ferrite powder adds the ferrous oxalate powder, become mixed-powder behind the ball milling, mixed-powder is filled in the sheet shape device mould, can add and be pressed into sheet shape device, after the sheet shape device low-temperature sintering: the nickel-copper-zinc ferrite sintered body, this sintered body has high resistivity, saturation magnetisation value is 62emu/g, and density is 4.693g/cm
3
Shown in Figure 2, for cleansing bath tub prepares coprecipitated liquid status figure, it is correct that want each connecting relation position, and operation set by step keeps clean.
Shown in Figure 3, be the vacuum filtration state diagram, bottle,suction 17 right parts are suction filter pump 18, bottle,suction 17 tops are Buchner funnel 19, in the Buchner funnel 19 is qualitative filter paper 23, and Buchner funnel 19 internal upper parts are that coprecipitated mixed liquor 21, bottom are product filter cake 20, and the bottom is a waste liquid 22 in the bottle,suction 17.
Shown in Figure 4, be nickel copper zinc ferrite powder calcined state figure, not calcining furnace 28 is outside for heater 24, right side are that pore 27, inside are furnace chamber 26 horse, and furnace chamber 26 centre positions are provided with ceramic product boat 25 and product powder 29.
Shown in Figure 5, be nickel-copper-zinc ferrite calcining heat and time coordinate graph of a relation, among the figure as can be known: temperature begins to heat up by 20 ℃, programming rate is 10 ℃/min, and temperature rises to 200 ℃, i.e. the A point, at this temperature constant temperature insulation 120min ± 10min, be A-B section, continue to be warming up to the C point then, promptly 800 ℃ ± 10 ℃, at this temperature calcining 120min ± 10min, be C-D section, be cooled to 20 ℃ ± 3 ℃ after the calcining, i.e. the E point.
Shown in Figure 6, for nickel copper zinc ferrite powder amplifies 100,000 times of product shape appearance figures, among the figure as can be known: product is the bronzing graininess, is irregular stacking, and ruler units is 100nm.
Shown in Figure 7, be nickel copper zinc ferrite powder diffracted intensity figure, among the figure as can be known: ordinate is the diffracted intensity index, and abscissa is the angle of diffraction 2 θ, has located a top at 35.34 °, corresponding (311).
Shown in Figure 8, be nickel-copper-zinc ferrite hysteresis curve figure, among the figure as can be known: ordinate is a magnetization value, and abscissa is a coercivity, the saturation magnetization height, remanent magnetization is lower, easily demagnetization, coercivity is very little.
Claims (5)
1, a kind of preparation method of nano nickel copper zinc ferrite powder, it is characterized in that: the chemical substance material that uses is nickelous sulfate, copper sulphate, zinc sulfate, ferrous sulfate, ammonium oxalate, deionized water, absolute ethyl alcohol, and its combination matching consumption is as follows: with gram, milliliter is measurement unit
Nickelous sulfate: NiSO
42.629g ± 0.001g
Copper sulphate: CuSO
42.500g ± 0.001g
Zinc sulfate: ZnSO
48.627g ± 0.001g
Ferrous sulfate: FeSO
427.805g ± 0.001g
Deionized water: H
2O 440ml ± 5ml
Absolute ethyl alcohol: C
2H
6O 50ml ± 2ml
Polyvinylpyrrolidone: [C
6H
9NO]
n0.670g ± 0.0005g
Ammonium oxalate: (NH
4)
2C
2O
425.582g ± 0.0001g
The preparation method is as follows:
(1) selected chemical substance material
The chemical substance material that preparation is used will carry out selected, and carries out purity control:
Magnetic acid nickel: 99.5%
Magnetic acid copper: 99.5%
Magnetic acid zinc: 99.5%
Magnetic acid is ferrous: 99.5%
Deionized water: 99.99%
Absolute ethyl alcohol: 99.7%
Polyvinylpyrrolidone: 99.9%
Ammonium oxalate: 99.8%
(2) preparing metal salt working solution
1. nickelous sulfate powder 2.629g ± 0.001g is placed beaker, add deionized water 13.3ml ± 0.1ml, stir 5min, become: nickel sulfate solution NiSO with agitator
46H
2O, mol ratio is 0.01mol;
2. copper sulphate powder 2.500g ± 0.001g is placed beaker, add deionized water 13.3ml ± 0.1ml, stir 5min, become: copper sulfate solution CuSO with agitator
45H
2O, mol ratio is 0.01mol;
3. zinc sulphate powder 8.627g ± 0.001g is placed beaker, add deionized water 40ml ± 0.4ml, stir 5min, become: zinc sulfate solution ZnSO with agitator
47H
2O, mol ratio is 0.03mol;
4. ferrous sulfate powder 27.805g ± 0.001g is placed beaker, add deionized water 133.3ml ± 1.4ml, stir 5min, become: ferrous sulfate aqueous solution FeSO with agitator
47H
2O, mol ratio is 0.1mol;
5. synthesis of metallic salt working solution
Nickel sulfate solution, copper sulfate solution, zinc sulfate solution, the ferrous sulfate aqueous solution of configuration are respectively placed the molten device of mixing, evenly stir 2min with oscillating agitator, make its mixing, become: nickelous sulfate+copper sulphate+zinc sulfate+ferrous sulfate quaternary mixed aqueous solution, standby;
(3) preparation ammonium oxalate precipitated liquid
25.582g ± 0.001g places beaker with ammonium oxalate, adds deionized water 240ml ± 2.4ml, stirs 10min with agitator, becomes: the ammonium oxalate aqueous solution (NH
4)
2C
2O
4H
2O, mol ratio is 0.18mol;
Add polyethylene of dispersing agent pyrrolidones 0.670g ± 0.0005g, and stir;
(4) coprecipitated reaction
1. the ammonium oxalate aqueous solution is placed four-hole boiling flask;
2. four-hole boiling flask is placed cleansing bath tub;
3. water-soluble cylinder is placed on the electric jacket;
4. insert thermometer, dropping funel, agitator, escape pipe on the four-hole boiling flask successively;
5. the ammonium oxalate aqueous solution is placed in the four-hole boiling flask, polyethylene of dispersing agent pyrrolidones 0.670g is Powdered herein, directly puts into when joining ammonium oxalate solution;
6. open the ammonium oxalate aqueous solution in electric jacket, heated water bath cylinder and the four-hole boiling flask, solution temperature rises to 50 ℃ ± 2 ℃;
7. drip the ambrose alloy zinc-iron quaternary aqueous solution
The quaternary aqueous solution is placed addition funnel, and rate of addition 10ml/min drips time 20min;
8. limit heating, limit drip, stir on the limit, and mixing speed 350r/min makes it fully mix, dissolve, time 120min ± 10min;
9. the concentration of metal sulfate and ammonium oxalate is 0.75mol/L, and the mol ratio of metal sulfate and ammonium oxalate is 1:1.2;
10. chemical reaction
Under ammonium oxalate aqueous solution heated condition, dripping under the quaternary mixed aqueous solution state, dripping under the polyethylene of dispersing agent pyrrolidones state, in whipping process chemical reaction will take place, reaction equation is as follows:
NiSO
4·6H
2O+CuSO
4·5H
2O+ZnSO
4·7H
2O+FeSO
47H
2O+(NH
4)
2
In the formula:
(NiCuZn) Fe
2(C
2O
4)
36H
2O: ambrose alloy zinc-iron oxalate mixtures
(5) vacuum filtration
Coprecipitated reacted mixed solution is placed Buchner funnel, Buchner funnel is placed on the vacuum filtration bottle;
In Buchner funnel, put three layers of middling speed qualitative filter paper, then coprecipitated reaction mixture is poured on the qualitative filter paper;
Open suction filter pump, waste liquid is evacuated in the filter flask, and the product filter cake is kept somewhere on the filter paper;
(6) washing, filtration
Absolute ethyl alcohol 10ml is placed on the product filter cake of funnel flushing, filtration;
Washing, filtration repeat 5 times;
(7) vacuum drying
Product filter cake after washing, the filtration is collected in the rustless steel container, and places vacuum drying chamber to carry out drying, vacuum is 1000Pa, and baking temperature is 80 ℃ ± 2 ℃, and be 1440min ± 10min drying time;
After the drying, get the product powder, that is: yellow, presoma product: ambrose alloy zinc-iron oxalate mixtures;
(8) calcining
The calcining of product powder is to carry out in the horizontal-type high temperature Muffle furnace;
The product powder is placed the ceramic product boat;
The product boat is placed Muffle furnace, and sealing;
Open not calcining furnace of horse, temperature rises to 200 ℃ by 20 ℃, 10 ℃/min of programming rate, at this temperature constant temperature insulation 120min ± 10min, eliminate micro-moisture and oxalates presoma in conjunction with water;
Continue to be warming up to 800 ℃ ± 10 ℃ then, 20 ℃/min of programming rate, constant temperature insulation 120min ± 10min:
Open calcining furnace, take out product boat and product powder;
Product boat and product powder are placed the pure air environment, naturally cool to 20 ℃ ± 3 ℃, get end product powder, that is: bronzing nickel copper zinc ferrite powder after the cooling;
To produce calcination reaction in sintering process, reaction equation is as follows:
In the formula: (NiC
uZ
n) Fe
2O
4: nickel copper zinc ferrite powder
CO
2: carbon dioxide
O: oxygen
(9) detect, chemically examine, analyze, characterize
Pattern, color and luster, composition, full phase constitution structure, Chemical Physics performance to the product powder of preparation are chemically examined, analyze, are characterized;
Carry out the analysis of oxalates presoma calcining and decomposing with differential thermal analysis meter;
Carry out the magnetic property analysis with vibrating specimen magnetometer;
Carrying out particle morphology with transmission electron microscope measures;
Carry out nickel-copper-zinc ferrite spinelle material phase analysis with X-ray diffractometer;
The product pattern is: bronzing, graininess powder, and the powder diameter is: 50-80nm; The full intensity of magnetization: the 52emu/g that closes;
(10) store
Nickel copper zinc ferrite powder to preparation places water white glass container, airtight storage, and clean environment wants waterproof, protection against the tide, acid-proof alkali salt to corrode 20 ℃ ± 3 ℃ of storage temperatures, relative humidity≤10%.
2, the preparation method of a kind of nano nickel copper zinc ferrite powder according to claim 1, it is characterized in that: the preparation of described nickel-copper-zinc ferrite is to be raw material with nickelous sulfate, copper sulphate, zinc sulfate, ferrous sulfate, with ammonium oxalate is coprecipitated dose, with the macromolecular material polyvinylpyrrolidone is dispersant, with the deionized water is solvent, is washing agent with the absolute ethyl alcohol.
3, the preparation method of a kind of nano nickel copper zinc ferrite powder according to claim 1, it is characterized in that: the calcining of described nickel copper zinc ferrite powder is carried out in the high temperature Muffle furnace, the micro-moisture evaporating temperature is 200 ℃ ± 10 ℃, the constant temperature temperature retention time is 120min ± 10min, calcining heat is 800 ℃ ± 10 ℃, and constant temperature insulation time of repose is 120min ± 10min.
4, the preparation method of a kind of nano nickel copper zinc ferrite powder according to claim 1 is characterized in that: the pattern of described nickel copper zinc ferrite powder is the bronzing powder, powder particle diameter 50-80nm, and saturation magnetization is 52emu/g.
5, the preparation method of a kind of nano nickel copper zinc ferrite powder according to claim 1, it is characterized in that: the coprecipitated reaction of described preparation nickel-copper-zinc ferrite is carried out in (3) at cleansing bath tub, four-hole boiling flask, the bottom of cleansing bath tub (1) is electric jacket (2), the top of cleansing bath tub (1) is four-hole boiling flask (3), four-hole boiling flask (3) top is provided with thermometer, dropping funel (5) and control valve (13), magnetic stirring apparatus (6), escape pipe (7) from left to right successively, and is reinforced by tapering plug (14) sealing; Electric jacket (2) is provided with LCDs (12), magnetic agitation controller (11), electric controller (10); The built-in bath water that discharges water of cleansing bath tub (1) (8), in the four-hole boiling flask (3) is ammonium oxalate solution, successively put polyvinylpyrrolidonesolution solution, ambrose alloy zinc-iron quaternary mixed solution (9) in the dropping funel (5), being added dropwise to complete the interior solution of back four-hole boiling flask (3) is: ammonium oxalate solution+ambrose alloy zinc-iron quaternary mixed liquor+polyvinylpyrrolidone aqueous solution, promptly coprecipitated solution; Escape pipe (7) is discharged carbon dioxide.
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| CN2009100736211A CN101456078B (en) | 2009-01-06 | 2009-01-06 | Preparation method of nano nickel copper zinc ferrite powder |
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| CN101973761A (en) * | 2010-09-15 | 2011-02-16 | 中北大学 | Method for preparing V2O5-adding NiCuZn ferrites |
| CN103008675A (en) * | 2012-12-19 | 2013-04-03 | 国家钽铌特种金属材料工程技术研究中心 | Preparation method of nickel coated copper composite powder |
| CN103641179A (en) * | 2013-11-29 | 2014-03-19 | 重庆市中工新材料有限公司 | Preparation method of iron composite oxide functional powder material |
| CN103978228A (en) * | 2014-05-28 | 2014-08-13 | 天津大学 | Preparation method of nano manganese ferrite electromagnetic wave absorbing material |
| CN104451956A (en) * | 2014-12-25 | 2015-03-25 | 南京理工大学常熟研究院有限公司 | Nano-ferrite alloy material |
| CN106180743A (en) * | 2016-08-23 | 2016-12-07 | 金川集团股份有限公司 | A kind of preparation method of fine fe-based alloy powder |
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| CN111671769A (en) * | 2020-05-26 | 2020-09-18 | 赣南医学院 | Application of copper-containing ferrite nano-particles in preparation of antitumor drugs |
| CN111773248A (en) * | 2020-05-26 | 2020-10-16 | 赣南医学院 | Copper-containing ferrite nano particle, preparation method and antibacterial action thereof |
| CN116041053A (en) * | 2022-11-30 | 2023-05-02 | 国网智能电网研究院有限公司 | Preparation method of honeycomb nickel-zinc ferrite material |
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| CN101973761A (en) * | 2010-09-15 | 2011-02-16 | 中北大学 | Method for preparing V2O5-adding NiCuZn ferrites |
| CN101973761B (en) * | 2010-09-15 | 2012-12-26 | 中北大学 | Method for preparing V2O5-adding NiCuZn ferrites |
| CN103008675A (en) * | 2012-12-19 | 2013-04-03 | 国家钽铌特种金属材料工程技术研究中心 | Preparation method of nickel coated copper composite powder |
| CN103641179A (en) * | 2013-11-29 | 2014-03-19 | 重庆市中工新材料有限公司 | Preparation method of iron composite oxide functional powder material |
| CN103978228A (en) * | 2014-05-28 | 2014-08-13 | 天津大学 | Preparation method of nano manganese ferrite electromagnetic wave absorbing material |
| CN104451956B (en) * | 2014-12-25 | 2016-08-24 | 南京理工大学常熟研究院有限公司 | A kind of nanometer ferrite alloy material |
| CN104451956A (en) * | 2014-12-25 | 2015-03-25 | 南京理工大学常熟研究院有限公司 | Nano-ferrite alloy material |
| CN106180743A (en) * | 2016-08-23 | 2016-12-07 | 金川集团股份有限公司 | A kind of preparation method of fine fe-based alloy powder |
| CN110255630A (en) * | 2019-07-24 | 2019-09-20 | 东北大学秦皇岛分校 | A kind of method that more metal salt solutions prepare metal oxide composite |
| CN110255630B (en) * | 2019-07-24 | 2021-10-08 | 东北大学秦皇岛分校 | Method for preparing metal oxide composite material by multi-metal salt solution |
| CN111671769A (en) * | 2020-05-26 | 2020-09-18 | 赣南医学院 | Application of copper-containing ferrite nano-particles in preparation of antitumor drugs |
| CN111773248A (en) * | 2020-05-26 | 2020-10-16 | 赣南医学院 | Copper-containing ferrite nano particle, preparation method and antibacterial action thereof |
| CN111671769B (en) * | 2020-05-26 | 2023-02-28 | 赣南医学院 | Application of copper-containing ferrite nano-particles in preparation of antitumor drugs |
| CN116041053A (en) * | 2022-11-30 | 2023-05-02 | 国网智能电网研究院有限公司 | Preparation method of honeycomb nickel-zinc ferrite material |
| CN116041053B (en) * | 2022-11-30 | 2024-03-26 | 国网智能电网研究院有限公司 | Preparation method of honeycomb nickel-zinc ferrite material |
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